KR20160067770A - Monophosphites comprising an anthrol - Google Patents

Monophosphites comprising an anthrol Download PDF

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KR20160067770A
KR20160067770A KR1020150171257A KR20150171257A KR20160067770A KR 20160067770 A KR20160067770 A KR 20160067770A KR 1020150171257 A KR1020150171257 A KR 1020150171257A KR 20150171257 A KR20150171257 A KR 20150171257A KR 20160067770 A KR20160067770 A KR 20160067770A
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alkyl
aryl
mmol
compound
toluene
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카트린 마리에 디발라
로베르트 프랑케
프랑크 가일렌
디르크 프리다크
디에테르 헤쓰
데틀레프 셀렌트
아르민 뵈르네르
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에보니크 데구사 게엠베하
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Abstract

Provided is monophosphite including anthrol. More specifically, the purpose of the present invention is to provide monophosphate which exhibits more favorable properties in a hydroformylation reaction than that of existing monophosphate.

Description

안트롤을 포함하는 모노포스파이트 {MONOPHOSPHITES COMPRISING AN ANTHROL}MONOPHOSPHITES COMPRISING AN ANTHROL < RTI ID = 0.0 >

본 발명은 안트롤을 포함하는 모노포스파이트에 관한 것이다. 또한, 히드로포르밀화에서의 리간드로서의 그의 용도에 관한 것이다.The present invention relates to a monophosphite comprising anthrol. It also relates to its use as a ligand in hydroformylation.

촉매의 존재 하에서 올레핀 화합물, 일산화탄소 및 수소 사이의 반응으로 하나의 추가의 탄소 원자를 포함하는 알데히드를 생성하는 것은 히드로포르밀화 또는 옥소 합성으로 공지되어 있다. 이들 반응에서, 원소 주기율표의 VIII족의 전이 금속의 화합물은 대개 촉매로서 채용된다. 공지된 리간드는 예를 들어 각각 3가 인 P(III)을 갖는 포스핀, 포스파이트 및 포스포나이트 부류로부터의 화합물이다. 올레핀 히드로포르밀화의 분야의 기술의 상태의 우수한 개관은 문헌 [B. CORNILS, W. A. HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", vol. 1 & 2, VCH, Weinheim, New York, 1996] 또는 [R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation", Chem. Rev., 2012, DOI:10.1021/cr3001803]에서 발견할 수 있다.The reaction between an olefinic compound, carbon monoxide and hydrogen in the presence of a catalyst to produce an aldehyde containing one additional carbon atom is known as hydroformylation or oxo synthesis. In these reactions, the compounds of transition metals of group VIII of the Periodic Table of the Elements are usually employed as catalysts. Known ligands are, for example, compounds from the phosphine, phosphite and phosphonite classes, each having trivalent P (III). An excellent overview of the state of the art in the field of olefin < RTI ID = 0.0 > hydroformylation < / RTI > CORNILS, W. A. HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds ", vol. 1 & 2, VCH, Weinheim, New York, 1996] or [R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation ", Chem. Rev., 2012, DOI: 10.1021 / cr3001803].

모든 촉매적 활성 조성물은 그의 특정 이점을 갖는다. 따라서, 공급원료 및 표적 생성물에 따라, 상이한 촉매적 활성 조성물이 사용된다.All catalytically active compositions have their particular advantages. Thus, depending on the feedstock and the target product, different catalytically active compositions are used.

EP 0 155 508 A1에는 입체 장해된 올레핀, 예를 들어 이소부텐의 로듐-촉매화된 히드로포르밀화에서 비스아릴렌-치환된 모노포스파이트의 용도가 개시되어 있다. 그러나, 여기에서 사용된 로듐 농도는 때로 매우 높고 (250 ppm인 것), 이는 로듐의 현재의 비용의 관점에서 공업적 규모 공정에 허용되지 않으며, 개선되어야 한다. 상기의 41면에는 3개의 페닐 라디칼이 각각 C-C 브리지를 통해 서로 부착되고, 이 경우 2,6-비페닐페놀 단위의 형태를 취하는 화합물이 나타나 있다.EP 0 155 508 A1 discloses the use of bisarylene-substituted monophosphites in rhodium-catalyzed hydroformylation of sterically hindered olefins, for example isobutene. However, the rhodium concentration used here is sometimes very high (250 ppm), which is not acceptable for industrial scale processes in terms of the current cost of rhodium and must be improved. On the above 41 sides, three phenyl radicals are attached to each other through a C-C bridge, in which case compounds appearing in the form of 2,6-biphenylphenol units are shown.

본 발명의 목적은 히드로포르밀화 반응에서 공지된 모노포스파이트에 비해 유리한 특성을 갖는 모노포스파이트를 제공하는 것이었다. 특히, 상기 목적은 비페놀 단위 외에 추가의 방향족 계를 가지며, 구조적으로 관련된 모노포스파이트의 사용에 비해 개선된 수율을 초래하는 신규한 리간드를 제공하는 것으로 이루어진다. 개선된 수율은 적어도 하나의 올레핀에 대해 달성되어야 한다.It was an object of the present invention to provide a monophosphite having properties advantageous over the known monophosphites in the hydroformylation reaction. In particular, this object is achieved by providing novel ligands which have an additional aromatic system besides biphenol units and which result in improved yields compared to the use of structurally related monophosphites. Improved yields should be achieved for at least one olefin.

100 ppm 미만의 금속 농도 (예를 들어 로듐)가 또한 요망된다.Metal concentrations of less than 100 ppm (e.g., rhodium) are also desired.

상기 목적은 청구항 1에 따른 화합물에 의해 달성된다.This object is achieved by the compound according to claim 1.

일반 구조 I 또는 II 중 하나를 갖는 화합물:Compounds having one of the general structures I or II:

<화학식 I>(I)

Figure pat00001
Figure pat00001

<화학식 II>&Lt;

Figure pat00002
Figure pat00002

상기 식에서,In this formula,

R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -CN, -NH2, -N[(C1-C12)-알킬]2로부터 선택되고; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -S-alkyl, -S-aryl, halogen, -COO- (C 1 -C 12 ) (C 1 -C 12 ) -alkyl, -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -SO 3 H, -CN, -NH 2, -N [( C 1 -C 12) - alkyl is selected from 2;

R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -NH2, -N[(C1-C12)-알킬]2로부터 선택되고; R 9, R 10, R 11 , R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl, halogen, -COO- (C 1 - C 12) - alkyl, -CONH- (C 1 -C 12) - alkyl, -CO- (C 1 -C 12) - alkyl, -CO- (C 6 -C 20) - aryl, -COOH, -OH , -SO 3 H, -NH 2, -N [(C 1 -C 12) - alkyl is selected from 2;

언급된 알킬 및 아릴 기는 치환될 수 있다.The alkyl and aryl groups mentioned may be substituted.

(C1-C12)-알킬 및 O-(C1-C12)-알킬은 각각 비치환되거나, (C3-C12)-시클로알킬, (C3-C12)-헤테로시클로알킬, (C6-C20)-아릴, 플루오린, 염소, 시아노, 포르밀, 아실 및 알콕시카르보닐로부터 선택되는 하나 이상의 동일하거나 상이한 라디칼에 의해 치환될 수 있다.(C 1 -C 12 ) -alkyl and O- (C 1 -C 12 ) -alkyl are each unsubstituted or substituted by one or more groups selected from (C 3 -C 12 ) -cycloalkyl, (C 3 -C 12 ) -heterocycloalkyl, (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl and alkoxycarbonyl.

(C6-C20)-아릴 및 -(C6-C20)-아릴-(C6-C20)-아릴-은 각각 비치환되거나, -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -할로겐 (예컨대 Cl, F, Br, I), -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -(C6-C20)-아릴-CON[(C1-C12)-알킬]2, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-알킬]2로부터 선택되는 하나 이상의 동일하거나 상이한 라디칼에 의해 치환될 수 있다. (C 6 -C 20 ) -aryl- and - (C 6 -C 20 ) -aryl- (C 6 -C 20 ) -aryl- are each unsubstituted or substituted by one or more substituents selected from the group consisting of -H, - (C 1 -C 12 ) -alkyl (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -halogen (such as Cl, F, Br, , -COO- (C 1 -C 12) - alkyl, -CONH- (C 1 -C 12) - alkyl, - (C 6 -C 20) - aryl -CON [(C 1 -C 12) - alkyl; 2, -CO- (C 1 -C 12 ) - alkyl, -CO- (C 6 -C 20) - aryl, -COOH, -OH, -SO 3 H , -SO 3 Na, -NO 2, -CN , -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2, and the like.

본 발명의 내용에서, 표현 "-(C1-C12)-알킬"은 직쇄 및 분지형 알킬 기를 포함한다. 바람직하게는, 이들 기는 비치환된 직쇄 또는 분지형 -(C1-C8)-알킬 기이고, 가장 바람직하게는 -(C1-C6)-알킬 기이다. -(C1-C12)-알킬 기의 예는 특히 메틸, 에틸, 프로필, 이소프로필, n-부틸, 이소부틸, sec-부틸, tert-부틸, n-펜틸, 2-펜틸, 2-메틸부틸, 3-메틸부틸, 1,2-디메틸프로필, 1,1-디메틸프로필, 2,2-디메틸프로필, 1-에틸프로필, n-헥실, 2-헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 1,1-디메틸부틸, 1,2-디메틸부틸, 2,2-디메틸부틸, 1,3-디메틸부틸, 2,3-디메틸부틸, 3,3-디메틸부틸, 1,1,2-트리메틸프로필, 1,2,2-트리메틸프로필, 1-에틸부틸, 1-에틸-2-메틸프로필, n-헵틸, 2-헵틸, 3-헵틸, 2-에틸펜틸, 1-프로필부틸, n-옥틸, 2-에틸헥실, 2-프로필헵틸, 노닐, 데실이다.In the context of the present invention, the expression &quot;-( C 1 -C 12 ) -alkyl "includes straight and branched alkyl groups. Preferably, these groups are unsubstituted straight-chain or branched- (C 1 -C 8 ) -alkyl groups and most preferably are - (C 1 -C 6 ) -alkyl groups. Examples of - (C 1 -C 12 ) -alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, Butyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, Dimethylbutyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, Methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propyl Butyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

표현 "-(C1-C12)-알킬"에 관한 설명은 또한 -O-(C1-C12)-알킬, 즉 -(C1-C12)-알콕시에서의 알킬 기에도 적용된다. 바람직하게는, 이들 기는 비치환된 직쇄 또는 분지형 -(C1-C6)-알콕시 기이다.The description of the expression "- (C 1 -C 12 ) -alkyl" also applies to -O- (C 1 -C 12 ) -alkyl, ie alkyl groups in- (C 1 -C 12 ) -alkoxy. Preferably, these groups are unsubstituted straight-chain or branched- (C 1 -C 6 ) -alkoxy groups.

치환된 -(C1-C12)-알킬 기 및 치환된 -(C1-C12)-알콕시 기는 그의 쇄 길이에 따라 하나 이상의 치환기를 가질 수 있다. 치환기는 바람직하게는 각각 독립적으로 -(C3-C12)-시클로알킬, -(C3-C12)-헤테로시클로알킬, -(C6-C20)-아릴, 플루오린, 염소, 시아노, 포르밀, 아실 및 알콕시카르보닐로부터 선택된다.Substituted - (C 1 -C 12) - alkyl group, and a substituted - (C 1 -C 12) - alkoxy group may have one or more substituents depending on its chain length. The substituents are preferably each independently selected from the group consisting of - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, Cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkylalkyl,

본 발명의 내용에서 표현 "-(C3-C12)-시클로알킬"은 3 내지 12개, 특히 5 내지 12개의 탄소 원자를 갖는 모노-, 비- 또는 트리시클릭 히드로카르빌 라디칼을 포함한다. 이들로는 시클로프로필-, 시클로부틸-, 시클로펜틸-, 시클로헥실-, 시클로헵틸-, 시클로옥틸-, 시클로도데실-, 시클로펜타데실-, 노르보르닐- 및 아다만틸을 들 수 있다. The term "- (C 3 -C 12 ) -cycloalkyl" in the context of the present invention includes mono-, non-or tricyclic hydrocarbyl radicals having 3 to 12, in particular 5 to 12 carbon atoms. These include cyclopropyl-, cyclobutyl-, cyclopentyl-, cyclohexyl-, cycloheptyl-, cyclooctyl-, cyclododecyl-, cyclopentadecyl-, norbornyl- and adamantyl.

치환된 시클로알킬의 한 예는 멘틸일 것이다.An example of a substituted cycloalkyl would be methyl.

본 발명의 내용에서 표현 "-(C3-C12)-헤테로시클로알킬 기"는 3 내지 12개, 특히 5 내지 12개의 탄소 원자를 갖는 비방향족 포화 또는 부분적 불포화 지환족 기를 포함한다. -(C3-C12)-헤테로시클로알킬 기는 바람직하게는 3 내지 8개, 보다 바람직하게는 5 또는 6개의 고리 원자를 갖는다. 헤테로시클로알킬 기에서, 시클로알킬 기와는 반대로, 1, 2, 3 또는 4개의 고리 탄소 원자는 헤테로원자 또는 헤테로원자-함유 기에 의해 대체된다. 헤테로원자 또는 헤테로원자-함유 기는 바람직하게는 -O-, -S-, -N-, -N(=O)-, -C(=O)- 및 -S(=O)-로부터 선택된다. -(C3-C12)-헤테로시클로알킬 기의 예는 테트라히드로티오페닐, 테트라히드로푸릴, 테트라히드로피라닐 및 디옥사닐이다. The term "- (C 3 -C 12 ) -heterocycloalkyl group" in the context of the present invention includes nonaromatic saturated or partially unsaturated alicyclic groups having 3 to 12, in particular 5 to 12, carbon atoms. - (C 3 -C 12) - heterocycloalkyl group is preferably 3 to 8, and more preferably have 5 or 6 ring atoms. In heterocycloalkyl groups, as opposed to cycloalkyl groups, one, two, three or four ring carbon atoms are replaced by a heteroatom or a heteroatom-containing group. The heteroatom or heteroatom-containing group is preferably selected from -O-, -S-, -N-, -N (= O) -, -C (= O) - and -S (= O) -. - (C 3 -C 12) - examples of heterocycloalkyl groups include the tetrahydro-thiophenyl, tetrahydrofuryl, tetrahydropyranyl and-dioxa-carbonyl.

본 발명의 내용에서, 표현 "-(C6-C20)-아릴 및 -(C6-C20)-아릴-(C6-C20)-아릴-"은 모노- 또는 폴리시클릭 방향족 히드로카르빌 라디칼을 포함한다. 이들은 6 내지 20개의 고리 원자, 보다 바람직하게는 6 내지 14개의 고리 원자, 특히 6 내지 10개의 고리 원자를 갖는다. 아릴은 바람직하게는 -(C6-C10)-아릴 및 -(C6-C10)-아릴-(C6-C10)-아릴-이다. 아릴은 특히 페닐, 나프틸, 인데닐, 플루오레닐, 안트라세닐, 페난트레닐, 나프타세닐, 크리세닐, 피레닐, 코로네닐이다. 보다 특히, 아릴은 페닐, 나프틸 및 안트라세닐이다.In the context of the present invention, the terms "- (C 6 -C 20 ) -aryl and - (C 6 -C 20 ) -aryl- (C 6 -C 20 ) -aryl-" refer to mono- or polycyclic aromatic hydrocarbons It contains a Vinyl radical. They have from 6 to 20 ring atoms, more preferably from 6 to 14 ring atoms, in particular from 6 to 10 ring atoms. Aryl is preferably - (C 6 -C 10 ) -aryl and - (C 6 -C 10 ) -aryl- (C 6 -C 10 ) -aryl-. Aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, or coronenyl. More particularly, aryl is phenyl, naphthyl, and anthracenyl.

치환된 -(C6-C20)-아릴 기 및 -(C6-C20)-아릴-(C6-C20)-아릴 기는 고리 크기에 따라 하나 이상의 (예를 들어 1, 2, 3, 4 또는 5개의) 치환기를 가질 수 있다. 이들 치환기는 바람직하게는 각각 독립적으로 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -할로겐 (예컨대 Cl, F, Br, I), -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -(C6-C20)-아릴-CON[(C1-C12)-알킬]2, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-알킬]2로부터 선택된다. (C 6 -C 20 ) -aryl- and (C 6 -C 20 ) -aryl- (C 6 -C 20 ) -aryl groups may optionally be substituted with one or more, for example 1, 2, 3 , 4 or 5) substituents. These substituents are preferably each independently selected from the group consisting of -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) (C 6 -C 20) - aryl, halogen (e.g. Cl, F, Br, I) , -COO- (C 1 -C 12) - alkyl, -CONH- (C 1 -C 12) - alkyl, - (C 6 -C 20) - aryl -CON [(C 1 -C 12) - alkyl] 2, -CO- (C 1 -C 12) - alkyl, -CO- (C 6 -C 20) - aryl, -COOH, -OH, -SO 3 H, -SO 3 Na, -NO 2, -CN, -NH 2, -N [(C 1 -C 12) - alkyl] 2 from Is selected.

치환된 -(C6-C20)-아릴 기 및 -(C6-C20)-아릴-(C6-C20)-아릴 기는 바람직하게는 치환된 -(C6-C10)-아릴 기 및 -(C6-C10)-아릴-(C6-C10)-아릴 기, 특히 치환된 페닐 또는 치환된 나프틸 또는 치환된 안트라세닐이다. 치환된 -(C6-C20)-아릴 기는 바람직하게는 -(C1-C12)-알킬 기, -(C1-C12)-알콕시 기로부터 선택되는 하나 이상의, 예를 들어 1, 2, 3, 4 또는 5개의 치환기를 갖는다.A substituted - (C 6 -C 20 ) -aryl group and a - (C 6 -C 20 ) -aryl- (C 6 -C 20 ) -aryl group are preferably substituted - (C 6 -C 10 ) group and a - (C 6 -C 10) - aryl - (C 6 -C 10) - aryl group, especially a substituted phenyl or substituted naphthyl or substituted anthracenyl. Substituted - (C 6 -C 20) - aryl group is preferably a - (C 1 -C 12) - alkyl group, - (C 1 -C 12) - contains at least one, selected from alkoxy groups in Example 1, 2, 3, 4 or 5 substituents.

한 실시양태에서, R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -N[(C1-C12)-알킬]2로부터 선택된다.In one embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 - C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl, halogen, -CO- (C 1 -C 12) -alkyl, -CO- (C 6 -C 20) - aryl, -N [(C 1 -C 12) -alkyl] 2 are selected from.

한 실시양태에서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -N[(C1-C12)-알킬]2로부터 선택된다.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are -H, - (C 1 -C 12 ) O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl, halogen, -CO - (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -N [(C 1 -C 12 ) -alkyl] 2 .

한 실시양태에서, R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐으로부터 선택된다.In one embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 - C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - is selected from aryl, -S- alkyl, -S- aryl, halogen.

한 실시양태에서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐으로부터 선택된다.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are -H, - (C 1 -C 12 ) Is selected from O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -S-alkyl, .

한 실시양태에서, R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴로부터 선택된다.In one embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 - C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - is selected from aryl, -S- alkyl, -S- aryl.

한 실시양태에서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴로부터 선택된다.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are -H, - (C 1 -C 12 ) Is selected from O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -S-alkyl, -S-aryl.

한 실시양태에서, R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴로부터 선택된다.In one embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 - C 12) - alkyl, -O- (C 6 -C 20) - is selected from aryl.

한 실시양태에서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴로부터 선택된다.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are -H, - (C 1 -C 12 ) O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl.

한 실시양태에서, R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬로부터 선택된다.In one embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 - C12 ) -alkyl. &Lt; / RTI &gt;

한 실시양태에서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬로부터 선택된다.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are -H, - (C 1 -C 12 ) O- (C 1 -C 12 ) -alkyl.

한 실시양태에서, 화합물은 하기 일반 구조 1 내지 10 중 하나를 갖는다.In one embodiment, the compound has one of the following general structures 1-10.

Figure pat00003
Figure pat00003

Figure pat00004
Figure pat00004

Figure pat00005
Figure pat00005

한 실시양태에서, 화합물은 일반 구조 I을 갖는다.In one embodiment, the compound has the general structure I.

한 실시양태에서, 화합물은 일반 구조 II를 갖는다.In one embodiment, the compound has the general structure II.

화합물 뿐만 아니라, 이들 화합물을 포함하는 착물도 또한 청구된다.Complexes comprising these compounds as well as compounds are also claimed.

- 상기 기재된 화합물,- the compounds described above,

- Rh, Ru, Co, Ir로부터 선택된 금속 원자- a metal atom selected from Rh, Ru, Co and Ir

를 포함하는 착물.&Lt; / RTI &gt;

바람직한 실시양태에서, 금속은 Rh이다.In a preferred embodiment, the metal is Rh.

이와 관련하여, 문헌 [R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation", Chem. Rev., 2012, DOI:10.1021/cr3001803; p. 5688, Scheme 12 "General Method for the Preparation of a P-Modified Rh precatalyst"] 및 그에 인용된 참고문헌, 및 또한 [P. W. N. M. van Leeuwen, in Rhodium Catalyzed Hydroformylation, P. W. N. M. van Leeuwen, C. Claver (eds.), Kluwer, Dordrecht, 2000, including p. 48 ff., p. 233 ff.] 및 그에 인용된 참고문헌, 및 또한 [K.D. Wiese and D. Obst in Top. Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg 2006 p. 6 ff.] 및 또한 그에 인용된 참고문헌을 참조한다.In this connection, see R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation ", Chem. Rev., 2012, DOI: 10.1021 / cr3001803; p. 5688, Scheme 12 "General Method for the Preparation of a P-Modified Rh precatalyst ", and references cited therein, and also [P. W. N. M. van Leeuwen, in Rhodium Catalyzed Hydroformylation, P. W. N. M. van Leeuwen, C. Claver (eds.), Kluwer, Dordrecht, 2000, including p. 48 ff., P. 233 ff.] And references cited therein, and also [K. Wiese and D. Obst in Top. Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg 2006 p. 6 ff.] And also references cited therein.

추가로, 히드로포르밀화 반응의 촉매작용을 위한 리간드-금속 착물에서의 리간드로서의 화합물의 용도가 청구된다.In addition, the use of a compound as a ligand in a ligand-metal complex for the catalysis of a hydroformylation reaction is claimed.

히드로포르밀화 반응의 촉매작용을 위한 리간드-금속 착물에서의 상기 기재된 화합물의 용도.Use of a compound as described above in a ligand-metal complex for the catalysis of a hydroformylation reaction.

화합물이 올레핀의 알데히드로의 전환을 위한 리간드-금속 착물에서 리간드로서 사용되는 방법이 또한 청구된다.Also claimed is a method wherein the compound is used as a ligand in a ligand-metal complex for the conversion of an olefin to an aldehyde.

하기 공정 단계:The following process steps:

a) 처음에 올레핀을 충전하는 단계;a) initially charging the olefin;

b) 상기 기재된 착물 또는 b) the complexes described above or

상기 기재된 화합물 및 Rh, Ru, Co, Ir로부터 선택된 금속 원자를 포함하는 물질A compound containing the above-described compound and a metal atom selected from Rh, Ru, Co, Ir

을 첨가하는 단계;Lt; / RTI &gt;

c) H2 및 CO를 공급하는 단계; 및c) supplying H 2 and CO; And

d) 반응 혼합물을 가열하여 올레핀을 알데히드로 전환시키는 단계d) heating the reaction mixture to convert the olefin to the aldehyde

를 포함하는 방법.&Lt; / RTI &gt;

이 방법에서, 공정 단계 a) 내지 d)는 임의의 바람직한 순서로 수행될 수 있다.In this method, process steps a) to d) may be performed in any desired order.

바람직한 공정의 변형에서, 금속 원자는 Rh이다.In a preferred process variant, the metal atom is Rh.

과량의 리간드는 또한 이 경우에 사용될 수 있으며, 각각의 리간드는 반드시 리간드-금속 착물의 형태로 결합한 채로 존재할 필요는 없고, 반응 혼합물 중에 유리 리간드로서 존재한다.Excess ligands can also be used in this case, and each ligand does not necessarily have to be bound in the form of a ligand-metal complex, and is present as a free ligand in the reaction mixture.

반응은 통상적인 조건 하에서 수행된다.The reaction is carried out under conventional conditions.

80℃ 내지 200℃의 온도 및 1 bar 내지 300 bar의 압력이 바람직하다.A temperature of 80 ° C to 200 ° C and a pressure of 1 bar to 300 bar are preferred.

100℃ 내지 160℃의 온도 및 15 bar 내지 250 bar의 압력이 특히 바람직하다.A temperature of 100 ° C to 160 ° C and a pressure of 15 bar to 250 bar are particularly preferred.

본 발명의 방법에서 히드로포르밀화를 위한 반응물은 말단 또는 내부 C-C 이중 결합을 갖는 2 내지 24개, 바람직하게는 3 내지 16개, 보다 바람직하게는 3 내지 12개의 탄소 원자를 갖는 올레핀 또는 올레핀의 혼합물, 특히 모노올레핀, 예를 들어 1-프로펜, 1- 또는 2-펜텐, 2-메틸-1-부텐, 2-메틸-2-부텐, 3-메틸-1-부텐, 1-, 2- 또는 3-헥센, 프로펜의 이량체화에서 수득되는 C6 올레핀 혼합물 (디프로펜), 헵텐, 2- 또는 3-메틸-1-헥센, 옥텐, 2-메틸헵텐, 3-메틸헵텐, 5-메틸-2-헵텐, 6-메틸-2-헵텐, 2-에틸-1-헥센, 부텐의 이량체화에서 수득되는 C8 올레핀 혼합물 (디부텐), 노넨, 2- 또는 3-메틸옥텐, 프로펜의 삼량체화에서 수득되는 C9 올레핀 혼합물 (트리프로펜), 데센, 2-에틸-1-옥텐, 도데센, 부텐의 사량체화 또는 삼량체화에서 수득되는 C12 올레핀 혼합물 (테트라프로펜 또는 트리부텐), 테트라데센, 헥사데센, 부텐의 사량체화에서 수득되는 C16 올레핀 혼합물 (테트라부탄), 및 상이한 수의 탄소 원자 (바람직하게는 2 내지 4개)를 갖는 올레핀의 공올리고머화에 의해 제조되는 올레핀 혼합물이다.In the process of the present invention, the reactants for hydroformylation are mixtures of olefins or olefins having from 2 to 24, preferably from 3 to 16, more preferably from 3 to 12 carbon atoms with terminal or internal CC double bonds , In particular monoolefins such as 1-propene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl- 3-hexene, Pro C 6 olefin mixture obtained in the dimerization of the pen (by dip pen), heptene, 2-or 3-methyl-1-hexene, octene, 2-heptene, 3-heptene, 5-methyl Heptene, 2-ethyl-1-hexene, a C 8 olefin mixture (dibutene) obtained by dimerization of butene, n-hexene, 2- or 3-methyl octene, A mixture of C 12 olefins obtained by trimerization or trimerization of a C 9 olefin mixture (tripropene), decene, 2-ethyl-1-octene, dodecene and butene obtained from trimerization In a tree-butene), tetradecene, hexadecene, C 16 olefin mixture obtained in the tetramerization solution heat of butene (tetrahydro-butane), and the carbon atom to a different number of (preferably an olefin having from 2 to 4) ball oligomerization &Lt; / RTI &gt;

이하, 본 발명을 제조 실시예에 의해 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to production examples.

일반적 작업 절차General Operation Procedures

이하의 모든 제조는 표준 슐렝크(Schlenk) 기법을 사용하여 보호 기체 하에서 수행하였다. 용매는 사용 전에 적합한 건조제 상에서 건조시켰다 (Purification of Laboratory Chemicals, W. L. F. Armarego (Author), Christina Chai (Author), Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009).All the following preparations were carried out under protective gas using standard Schlenk techniques. The solvent was dried on a suitable desiccant prior to use (W. L. F. Armarego (Author), Christina Chai (Author), Butterworth Heinemann (Elsevier, 6th edition, Oxford 2009).

삼염화인 (알드리치(Aldrich))를 사용 전에 아르곤 하에서 증류시켰다. 모든 제조 작업은 소부된(baked-out) 용기에서 수행하였다. 생성물은 NMR 분광분석법에 의해 특성화하였다. 화학적 이동 (δ)은 ppm으로 기록하였다. 31P NMR 신호는 SR31P = SR1H * (BF31P / BF1H) = SR1H * 0.4048에 따라 언급하였다 (Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow, and Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818; Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem., 2008, 80, 59-84).Phosphorus trichloride (Aldrich) was distilled under argon prior to use. All manufacturing operations were performed in a baked-out vessel. The product was characterized by NMR spectroscopy. Chemical shifts (δ) were reported in ppm. The 31 P NMR signal was noted according to SR 31P = SR 1H * (BF 31P / BF 1H ) = SR 1H * 0.4048 (Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow, and Pierre Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem. , 2008, 80, 59-84).

핵 공명 스펙트럼의 기록은 브루커 어드밴스(Bruker Avance) 300 또는 브루커 어드밴스 400 상에서, 기체 크로마토그래피 분석은 애질런트(Agilent) GC 7890A 상에서, 원소 분석은 레코 트루스펙(Leco TruSpec) CHNS 및 배리언 (Varian) ICP-OES 715 상에서, ESI-TOF 질량 분광측정법은 써모 일렉트론 피니간(Thermo Electron Finnigan) MAT 95-XP 및 애질런트 6890 N/5973 기기 상에서 수행하였다.Nuclear resonance spectra were recorded on a Bruker Avance 300 or Bruker Advance 400, gas chromatographic analysis on an Agilent GC 7890A, elemental analysis using Leco TruSpec CHNS and Varian ) On ICP-OES 715, ESI-TOF mass spectrometry was performed on a Thermo Electron Finnigan MAT 95-XP and Agilent 6890 N / 5973 instrument.

비페놀Biphenol

비피놀은 DE102013203865 및 DE102013203867과 유사하게 합성한다.Bifinol is synthesized analogously to DE102013203865 and DE102013203867.

클로로포스파이트의 합성Synthesis of chlorophosphite

모노- 및 디클로로포스파이트, 예컨대 (안트라센-9-일옥시)디클로로포스핀, 2,6-디페닐페녹시디클로로포스핀 또는 6-클로로디벤조[d,f][1,3,2]디옥사포스페핀의 합성은 관련 기술분야의 통상의 기술자에게 공지되어 있으며, 공지된 방식으로 수행한다. 클로로포스파이트는 삼아염소산인을 염기의 존재 하에서 첨가함으로써 제조할 수 있다. 상세한 정보를 위해, 또한 문헌 ["Phosphorous(III) Ligands in Homogeneous Catalysis - Design and Synthesis" by Paul C.J. Kamer and Piet W.N.M. van Leeuwen; John Wiley and Sons, 2012; including p. 94 ff.] 및 그에 인용된 참고문헌을 참조한다.Mono- and dichlorophosphites such as (anthracene-9-yloxy) dichlorophosphine, 2,6-diphenylphenoxydichlorophosphine or 6-chlorodibenzo [d, f] [1,3,2] di The synthesis of oxophosphines is known to those of ordinary skill in the relevant art and is carried out in a known manner. Chlorophosphites can be prepared by adding phosphorus trioxide in the presence of a base. For further information, see also "Phosphorous (III) Ligands in Homogeneous Catalysis - Design and Synthesis" by Paul C.J. Kamer and Piet W.N.M. van Leeuwen; John Wiley and Sons, 2012; including p. 94 ff.] And references cited therein.

모노포스파이트의 합성Synthesis of monophosphite

6-(안트라센-9-일옥시)디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) dibenzo [d, f] [1,3,2] dioxaphosphper.

Figure pat00006
Figure pat00006

톨루엔 (9 ml) 중 안트라센-9-올 (0.389 g; 2.00 mmol)의 교반 용액에 트리에틸아민 (1.858 g; 18.36 mmol)을 첨가하고, 생성된 혼합물을 0℃에서 톨루엔 (9 ml) 중 6-클로로디벤조[d,f][1,3,2]디옥사포스페핀 (0.501 g; 2.00 mmol)의 용액에 적가하였다. 반응 혼합물을 밤새 교반하고, 여과하였다. 여과물을 진공 하에서 농축 건조시켰다. 생성된 고체를 40℃에서 2시간 동안 건조시킨 후, 고온 디클로로메탄 (3 ml)으로부터 재결정화하였다. 수율: 0.206 g (0.504 mmol; 25%).To the stirred solution of anthracene-9-ol (0.389 g; 2.00 mmol) in toluene (9 ml) was added triethylamine (1.858 g; 18.36 mmol) and the resulting mixture was added to a solution of 6 -Chlorodibenzo [d, f] [l, 3,2] dioxaphosphepin (0.501 g; 2.00 mmol) in THF. The reaction mixture was stirred overnight and filtered. The filtrate was concentrated to dryness under vacuum. The resulting solid was dried at 40 &lt; 0 &gt; C for 2 h and then recrystallized from hot dichloromethane (3 ml). Yield: 0.206 g (0.504 mmol; 25%).

Figure pat00007
Figure pat00007

6-(안트라센-9-일옥시)-4,8-디-tert-부틸-2,10-디메톡시디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -4,8-di-tert-butyl-2,10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphepin.

Figure pat00008
Figure pat00008

톨루엔 (9 ml) 중 안트라센-9-올 (0.388 g; 2 mmol)의 교반 용액에 트리에틸아민 (1.854 g; 18.33 mmol)을 첨가하고, 생성된 혼합물을 0℃에서 톨루엔 (8 ml) 중 4,8-디-tert-부틸-6-클로로-2,10-디메톡시디벤조[d,f][1,3,2]디옥사포스페핀 (0.845 g; 2 mmol)의 용액에 적가하였다. 반응 혼합물을 밤새 교반하고, 여과하였다. 여과물을 진공 하에서 농축 건조시켰다. 얻어진 잔류물을 헥산 (4 ml 각각)과 함께 2회 교반하고, 여과한 후, 진공 하에서 건조시켰다. 수율: 0.206 g (0.355 mmol; 18%).To the stirred solution of anthracene-9-ol (0.388 g; 2 mmol) in toluene (9 ml) was added triethylamine (1.854 g; 18.33 mmol) and the resulting mixture was added to a solution of 4 Was added dropwise to a solution of 8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphepin (0.845 g; The reaction mixture was stirred overnight and filtered. The filtrate was concentrated to dryness under vacuum. The resulting residue was stirred twice with hexane (each of 4 ml), filtered and then dried under vacuum. Yield: 0.206 g (0.355 mmol; 18%).

Figure pat00009
Figure pat00009

6-(안트라센-9-일옥시)-2,4,8,10-테트라-tert-부틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin.

Figure pat00010
Figure pat00010

톨루엔 (7 ml) 중 안트라센-9-올 (0.281 g; 1.45 mmol)의 교반 현탁액에 트리에틸아민 (1.344 g; 13.28 mmol)을 첨가하고, 생성된 혼합물을 0℃에서 톨루엔 (6 ml) 중 2,4,8,10-테트라-tert-부틸-6-클로로디벤조[d,f][1,3,2]디옥사포스페핀 (0.724 g; 1.52 mmol)의 용액에 적가하였다. 반응 혼합물을 밤새 교반하고, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 생성된 잔류물을 헥산 (4 ml)으로부터 재결정화하였다. 수율: 0.559 g (0.883 mmol; 61%).To the stirred suspension of anthracene-9-ol (0.281 g; 1.45 mmol) in toluene (7 ml) was added triethylamine (1.344 g; 13.28 mmol) and the resulting mixture was added to a solution of 2 , 4,8,8-tetra-tert-butyl-6-chlorodibenzo [d, f] [1,3,2] dioxaphosphepin (0.724 g; 1.52 mmol). The reaction mixture was stirred overnight and filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was recrystallized from hexane (4 ml). Yield: 0.559 g (0.883 mmol; 61%).

Figure pat00011
Figure pat00011

6-(안트라센-9-일옥시)-4-메톡시-2-메틸벤조[d]나프토[1,2-f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -4-methoxy-2-methylbenzo [d] naphtho [l, 2-f] [1,3,2] dioxaphosphper.

Figure pat00012
Figure pat00012

THF (8 ml) 중 1-(2-히드록시-3-메톡시-5-메틸페닐)나프탈렌-2-올 (0.448 g; 1.598 mmol)의 용액에 피리딘 (0.284 g; 3.596 mmol)을 첨가하였다. 그 후, THF (6 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.472 g; 1.598 mmol)의 용액을 0℃에서 적가하였다. 반응 혼합물을 밤새 교반하고, 여과하고, 여과물을 진공 하에서 농축 건조시켰다. 얻어진 잔류물을 고온 디클로로메탄 (13 ml)으로부터 재결정화하였다. 수율: 0.302 g (0.601 mmol; 38%).To a solution of l- (2-hydroxy-3-methoxy-5-methylphenyl) naphthalen-2-ol (0.448 g; 1.598 mmol) in THF (8 ml) was added pyridine (0.284 g; 3.596 mmol). A solution of (anthracene-9-yloxy) dichlorophosphine (0.472 g; 1.598 mmol) in THF (6 ml) was then added dropwise at 0 占 폚. The reaction mixture was stirred overnight, filtered and the filtrate was concentrated to dryness under vacuum. The resulting residue was recrystallized from hot dichloromethane (13 ml). Yield: 0.302 g (0.601 mmol; 38%).

Figure pat00013
Figure pat00013

6-(안트라센-9-일옥시)-9-(tert-부틸)-4-메톡시-2-메틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -9- (tert-butyl) -4-methoxy-2-methyldibenzo [d, f] [1,3,2] dioxaphosphper.

Figure pat00014
Figure pat00014

톨루엔 (7 ml) 중 4'-(tert-부틸)-3-메톡시-5-메틸-[1,1'-비페닐]-2,2'-디올 (0.703 g; 2.46 mmol)의 교반 현탁액에 트리에틸아민 (2.277 g; 22.50 mmol)을 첨가하고, 이 혼합물을 0℃에서 톨루엔 (13 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.725 g; 2.46 mmol)의 용액에 적가하였다. 반응 혼합물을 밤새 교반한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 생성된 잔류물을 톨루엔 (2 ml)으로부터 재결정화하였다. 수율: 0.320 g (0.630 mmol; 26%).To a stirred suspension of 4 '- (tert-butyl) -3-methoxy-5-methyl- [1,1'- biphenyl] -2,2'-diol (0.703 g; 2.46 mmol) in toluene (2.277 g; 22.50 mmol) and the mixture was added dropwise to a solution of (anthracene-9-yloxy) dichlorophosphine (0.725 g; 2.46 mmol) in toluene (13 ml) at 0 ° C . The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was recrystallized from toluene (2 ml). Yield: 0.320 g (0.630 mmol; 26%).

Figure pat00015
Figure pat00015

6-(안트라센-9-일옥시)-2-이소프로필-8-메톡시-3,10-디메틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -2-isopropyl-8-methoxy-3,10-dimethyldibenzo [d, f] [1,3,2] dioxaphosphper.

Figure pat00016
Figure pat00016

톨루엔 (7 ml) 중 5'-이소프로필-3-메톡시-4',5-디메틸-[1,1'-비페닐]-2,2'-디올 (0.359 g; 1.252 mmol)의 용액에 트리에틸아민 (1.161 g; 11.473 mmol)을 첨가하고, 0℃로 냉각시키고, 이 혼합물에 톨루엔 (9 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.370 g; 1.252 mmol)의 용액을 적가하였다. 반응 혼합물을 밤새 교반한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시켰다. 수율: 0.594 g (1.168 mmol; 93%).To a solution of 5'-isopropyl-3-methoxy-4 ', 5-dimethyl- [1,1'-biphenyl] -2,2'-diol (0.359 g; 1.252 mmol) in toluene (7 ml) (1.161 g; 11.473 mmol) was added and the mixture was cooled to 0 ° C and a solution of (anthracene-9-yloxy) dichlorophosphine (0.370 g; 1.252 mmol) in toluene (9 ml) . The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated to dryness under vacuum. Yield: 0.594 g (1.168 mmol; 93%).

Figure pat00017
Figure pat00017

6-(안트라센-9-일옥시)-4-메톡시-2,10-디메틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -4-methoxy-2,10-dimethyldibenzo [d, f] [1,3,2] dioxaphosphper.

Figure pat00018
Figure pat00018

톨루엔 (16 ml) 중 3-메톡시-5,5'-디메틸-[1,1'-비페닐]-2,2'-디올 (0.655 g; 2.68 mmol)의 교반 용액에 트리에틸아민 (2.487 g; 24.58 mmol)을 첨가하고, 혼합물을 0℃로 냉각시켰다. 이 혼합물에 톨루엔 (18 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.792 g; 2.683 mmol)의 용액을 적가하였다. 반응 혼합물을 밤새 교반한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 잔류물을 50℃ / 0.1 mbar에서 3시간 동안 건조시켰다. 수율: 1.020 g (2.187 mmol; 82%).To a stirred solution of 3-methoxy-5,5'-dimethyl- [1,1'-biphenyl] -2,2'-diol (0.655 g; 2.68 mmol) in toluene (16 ml) was added triethylamine g; 24.58 mmol) was added and the mixture was cooled to 0 &lt; 0 &gt; C. To this mixture was added dropwise a solution of (anthracene-9-yloxy) dichlorophosphine (0.792 g; 2.683 mmol) in toluene (18 ml). The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated to dryness under vacuum, and the residue was dried at 50 [deg.] C / 0.1 mbar for 3 hours. Yield: 1.020 g (2.187 mmol; 82%).

Figure pat00019
Figure pat00019

6-(안트라센-9-일옥시)-4-메톡시-2,8,10-트리메틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -4-methoxy-2,8,10-trimethyldibenzo [d, f] [l, 3,2] dioxaphosphepin.

Figure pat00020
Figure pat00020

톨루엔 (9 ml) 중 3-메톡시-3',5,5'-트리메틸-[1,1'-비페닐]-2,2'-디올 (0.409 g; 1.58 mmol)의 용액에 트리에틸아민 (2.468 g; 14.51 mmol)을 첨가하고, 0℃로 냉각시키고, 이 혼합물에 톨루엔 (11 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.467 g; 1.584 mmol)의 용액을 적가하였다. 반응 혼합물을 밤새 교반한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 생성된 잔류물을 헥산 (17 ml)으로부터 재결정화하였다. 수율: 0.511 g (1.063 mmol; 67%).To a solution of 3-methoxy-3 ', 5,5'-trimethyl- [1,1'-biphenyl] -2,2'-diol (0.409 g; 1.58 mmol) in toluene (9 ml) (2.468 g; 14.51 mmol) was added, cooled to 0 ° C, and a solution of (anthracene-9-yloxy) dichlorophosphine (0.467 g; 1.584 mmol) in toluene (11 ml) was added dropwise to the mixture. The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was recrystallized from hexane (17 ml). Yield: 0.511 g (1.063 mmol; 67%).

Figure pat00021
Figure pat00021

6-(안트라센-9-일옥시)-8-메톡시-2,3,10-트리메틸디벤조[d,f][1,3,2]디옥사포스페핀.6- (Anthracene-9-yloxy) -8-methoxy-2,3,10-trimethyldibenzo [d, f] [1,3,2] dioxaphosphper.

Figure pat00022
Figure pat00022

톨루엔 (11 ml) 중 3-메톡시-4',5,5'-트리메틸-[1,1'-비페닐]-2,2'-디올 (0.518 g; 2.00 mmol)의 용액에 트리에틸아민 (1.857 g; 18.35 mmol)을 첨가하고, 혼합물을 0℃로 냉각시켰다. 이 혼합물에 톨루엔 (8 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.591 g; 2.00 mmol)의 용액을 적가하였다. 추가의 톨루엔 (30 ml)을 첨가한 후, 반응 혼합물을 밤새 교반하였다. 그 후, 혼합물을 여과하고, 용매를 진공 하에서 제거하였다. 얻어진 잔류물을 톨루엔 (11 ml)에 흡수시키고, 생성된 현탁액을 온건하게 가열한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 얻어진 잔류물을 50℃ / 0.1 mbar에서 건조시켰다. 수율: 0.489 g (1.018 mmol; 51%).To a solution of 3-methoxy-4 ', 5,5'-trimethyl- [1,1'-biphenyl] -2,2'-diol (0.518 g; 2.00 mmol) in toluene (11 ml) (1.857 g; 18.35 mmol) and the mixture was cooled to 0 &lt; 0 &gt; C. To this mixture was added dropwise a solution of (anthracene-9-yloxy) dichlorophosphine (0.591 g; 2.00 mmol) in toluene (8 ml). After addition of additional toluene (30 ml), the reaction mixture was stirred overnight. The mixture was then filtered and the solvent removed in vacuo. The resulting residue was taken up in toluene (11 ml) and the resulting suspension was heated gently and filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was dried at 50 [deg.] C / 0.1 mbar. Yield: 0.489 g (1.018 mmol; 51%).

Figure pat00023
Figure pat00023

6-(안트라센-9-일옥시)-4-(tert-부틸)-2-메톡시벤조[d]나프토[1,2-f][1,3,2]디옥사포스페핀.6- (Anthracen-9-yloxy) -4- (tert-butyl) -2-methoxybenzo [d] naphtho [l, 2-f] [1,3,2] dioxaphosphper.

Figure pat00024
Figure pat00024

톨루엔 (14 ml) 중 1-(3-(tert-부틸)-2-히드록시-5-메톡시페닐)나프탈렌-2-올 (0.730 g; 2.26 mmol)의 용액에 트리에틸아민 (2.097 g; 20.73 mmol)을 첨가하고, 이 혼합물에 0℃에서 톨루엔 (10 ml) 중 (안트라센-9-일옥시)디클로로포스핀 (0.668 g; 2.26 mmol)의 용액을 적가하였다. 반응 혼합물을 밤새 교반한 후, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 생성된 잔류물을 헥산 (28 ml)으로부터 재결정화하였다. 수율: 0.708 g (1.30 mmol; 58%).To a solution of 1- (3- (tert-butyl) -2-hydroxy-5-methoxyphenyl) naphthalen-2-ol (0.730 g; 2.26 mmol) in toluene (14 ml) was added triethylamine (2.097 g; 20.73 mmol) was added and a solution of (anthracene-9-yloxy) dichlorophosphine (0.668 g; 2.26 mmol) in toluene (10 ml) was added dropwise to the mixture at 0 ° C. The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was recrystallized from hexane (28 ml). Yield: 0.708 g (1.30 mmol; 58%).

Figure pat00025
Figure pat00025

6-([1,1':3',1''-테르페닐]-2'-일옥시)-4,8-디-tert-부틸-2,10-디메톡시디벤조[d,f][1,3,2]디옥사포스페핀.Di [tert-butyl-2, 10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphepine.

(비교용 화합물)(Comparative compound)

Figure pat00026
Figure pat00026

톨루엔 (8 ml) 중 2,6-디페닐페놀 (0.411 g; 1.65 mmol)의 용액에 트리에틸아민 (1.529 g; 15.11 mmol)을 첨가하고, 생성된 혼합물을 0℃에서 톨루엔 (6 ml) 중 4,8-디-tert-부틸-6-클로로-2,10-디메톡시디벤조[d,f][1,3,2]디옥사포스페핀 (0.697 g; 1.65 mmol)의 용액에 적가하였다. 반응 혼합물을 실온에서 밤새 및 70℃에서 5시간 동안 교반하였다. 그 후, 혼합물을 여과하고, 여과물을 진공 하에서 농축 건조시켰다. 얻어진 잔류물을 헥산 (4 ml)으로부터 재결정화하였다. 수율: 0.417 g (0.659 mmol; 40%).To the solution of 2,6-diphenylphenol (0.411 g; 1.65 mmol) in toluene (8 ml) was added triethylamine (1.529 g; 15.11 mmol) and the resulting mixture was added to a solution of Was added dropwise to a solution of 4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphepin (0.697 g; . The reaction mixture was stirred at room temperature overnight and at 70 &lt; 0 &gt; C for 5 hours. The mixture was then filtered and the filtrate was concentrated to dryness under vacuum. The resulting residue was recrystallized from hexane (4 ml). Yield: 0.417 g (0.659 mmol; 40%).

Figure pat00027
Figure pat00027

6-([1,1':3',1''-테르페닐]-2'-일옥시)-2,4,8,10-테트라-tert-부틸디벤조[d,f][1,3,2]디옥사포스페핀.F, [1, 3 ', 1 "-terphenyl] -2'-yloxy) -2,4,8,10-tetra-butyldibenzo [d, 3,2] dioxaphosphepine.

(비교용 화합물)(Comparative compound)

Figure pat00028
Figure pat00028

톨루엔 (13 ml) 중 3,3',5,5'-테트라-tert-부틸-[1,1'-비페닐]-2,2'-디올 (0.616 g; 1.50 mmol)의 용액에 트리에틸아민 (1.390 g; 13.74 mmol)을 첨가하고, 혼합물을 0℃로 냉각시켰다. 이 혼합물에 톨루엔 (3 ml) 중 (2,6-디페닐페녹시)디클로로포스핀 (0.521 g; 1.50 mmol)의 용액을 적가하였다. 반응 혼합물을 밤새 교반하고, 여과하였다. 여과물을 진공 하에서 농축 건조시키고, 생성된 잔류물을 디클로로메탄 (3 ml)에 흡수시키고, 실리카 겔 상에서 여과하였다. 여과물을 진공 하에서 농축시키고, 얻어진 고체를 50℃ / 0.1 mbar에서 건조시켰다. 수율: 0.955 g (1.394 mmol; 93%).To a solution of 3,3 ', 5,5'-tetra-tert-butyl- [1,1'-biphenyl] -2,2'-diol (0.616 g; 1.50 mmol) in toluene (13 ml) Amine (1.390 g; 13.74 mmol) was added and the mixture was cooled to 0 &lt; 0 &gt; C. To this mixture was added dropwise a solution of (2,6-diphenylphenoxy) dichlorophosphine (0.521 g; 1.50 mmol) in toluene (3 ml). The reaction mixture was stirred overnight and filtered. The filtrate was concentrated to dryness under vacuum and the resulting residue was taken up in dichloromethane (3 ml) and filtered over silica gel. The filtrate was concentrated in vacuo and the resulting solid was dried at 50 [deg.] C / 0.1 mbar. Yield: 0.955 g (1.394 mmol; 93%).

Figure pat00029
Figure pat00029

촉매작용 실험을 위한 절차Procedures for catalysis experiments

히드로포르밀화를 스위스 렝가우 소재의 프레멕스 리엑터 아게(Premex Reactor AG)로부터의 압력-유지 장치, 기체 유량계, 살포 교반기 및 압력 피펫이 구비된 200 ml 오토클레이브에서 수행하였다. 수분 및 산소의 영향을 최소화하기 위해, 용매로서 사용되는 톨루엔을 나트륨 케틸로 건조시키고, 아르곤 하에서 증류시켰다. 사용된 올레핀은 옥텐 혼합물이었다: n-옥텐 (옥세노 게엠베하(Oxeno GmbH), 1-옥텐: 약 3%; 시스+트랜스-2-옥텐; 약 49%; 시스+트랜스-3-옥텐: 약 29%; 시스+트랜스-4-옥텐: 약 16%; 구조적 이성질체 옥텐: 약 3%의 옥텐 이성질체의 혼합물)을 환류 하에서 수 시간 동안 나트륨 상에서 가열하고, 아르곤 하에서 증류시켰다.Hydroformylation was carried out in a 200 ml autoclave equipped with a pressure-holding device, a gas flow meter, a spraying stirrer and a pressure pipette from Premex Reactor AG, Lenggou, Switzerland. To minimize the effects of moisture and oxygen, the toluene used as solvent was dried over sodium kettle and distilled under argon. The olefin used was an octene mixture: n-octene (Oxeno GmbH, 1-octene: about 3%; cis + trans-2-octene about 49% 29%; cis + trans-4-octene: about 16%; structural isomeric octene: mixture of about 3% octenoisomer) was heated under reflux over sodium for several hours and distilled under argon.

실험을 위해, 톨루엔 중 촉매 전구체로서의 [(acac)Rh(COD)] (acac = 아세틸아세토네이트 음이온; COD = 1,5-시클로옥타디엔, 우미코어 (Umicore)) 형태의 로듐의 하기 용액을 오토클레이브 내로 아르곤 분위기 하에서 도입하였다: 로듐 100 질량 ppm에서의 실험을 위해, 4.31 밀리몰 용액 10 ml, 40 또는 60 질량 ppm을 위해, 동일한 양의 적절하게 희석된 용액. 그 후, 톨루엔에 용해된 적절한 양의 포스파이트 화합물 (로듐 당 5 리간드 당량)을 첨가하였다. 추가의 톨루엔을 첨가함으로써 (톨루엔의 총량은 GC 분석을 위해 측정하였음, 하기 참조), 촉매 용액의 초기 부피를 41.0 ml로 조정하였다. 도입되는 톨루엔의 질량을 각 경우에 측정하였다. n-옥텐의 중량: 10.70 g (95.35 mmol). 오토클레이브를 각 경우에 제시된 온도로 a) 50 bar의 최종 압력을 위해 42 bar, 또는 b) 20 bar의 최종 압력을 위해 12 bar의 총 기체 압력 (합성 기체: 린데(Linde); H2 (99.999%) : CO (99.997%) = 1 : 1)에서 교반하면서 (1500 rpm) 가열하였다. 반응 온도에 도달한 후, 합성 기체 압력이 a) 50 bar의 최종 압력을 위해 48.5 bar, 또는 b) 20 bar의 최종 압력을 위해 19.5 bar로 증가되었고, 반응물을 약 3 bar의 양압 하에서 압력 피펫에 세팅하여 도입하였다. 반응을 각각 50 또는 20 bar의 일정한 압력 (네덜란드 소재의 브론크호르스트(Bronkhorst)로부터의 폐쇄-루프 압력 제어기)에서 4시간에 걸쳐 수행하였다. 반응 시간이 경과된 후, 오토클레이브를 실온으로 냉각시키고, 교반하면서 감압시키고, 아르곤으로 퍼징하였다. 각 반응 혼합물 1 ml를 교반기가 꺼진 직후 빼내어, 펜탄 5 ml로 희석하고, 기체 크로마토그래피에 의해 분석하였다: HP 5890 시리즈 II 플러스, PONA, 50 m x 0.2 mm x 0.5 μm. 잔류 올레핀 및 알데히드의 정량적 측정을 내부 표준물로서의 용매 톨루엔을 참고로 하여 수행하였다.For the experiment, the following solution of rhodium in the form of [(acac) Rh (COD)] (acac = acetylacetonate anion; COD = 1,5-cyclooctadiene, Umicore) as a catalyst precursor in toluene Were introduced into the clave under an argon atmosphere: for the experiment at 100 mass ppm of rhodium, the same amount of a suitably diluted solution, for 10 ml of a 4.31 mmol solution, 40 or 60 mass ppm. A suitable amount of phosphite compound (5 ligand equivalents per rhodium) dissolved in toluene was then added. By adding additional toluene (the total amount of toluene was measured for GC analysis, see below), the initial volume of the catalyst solution was adjusted to 41.0 ml. The mass of toluene introduced was measured in each case. Weight of n-octene: 10.70 g (95.35 mmol). The autoclave was heated to the temperatures indicated in each case a) 42 bar for a final pressure of 50 bar, or b) a total gas pressure of 12 bar for a final pressure of 20 bar (synthetic gas: Linde; H 2 (99.999 %): CO (99.997%) = 1: 1) with stirring (1500 rpm). After reaching the reaction temperature, the synthesis gas pressure was increased to a) 48.5 bar for a final pressure of 50 bar, or b) 19.5 bar for a final pressure of 20 bar, and the reaction was pumped to a pressure pipette . The reaction was carried out over a period of 4 hours at a constant pressure of 50 or 20 bar each (closed-loop pressure controller from Bronkhorst, The Netherlands). After the reaction time had elapsed, the autoclave was cooled to room temperature, reduced in pressure with stirring and purged with argon. Immediately after the stirrer was turned off, 1 ml of each reaction mixture was diluted with 5 ml of pentane and analyzed by gas chromatography: HP 5890 Series II Plus, PONA, 50 mx 0.2 mm x 0.5 μm. Quantitative determination of residual olefins and aldehydes was carried out with reference to the solvent toluene as internal standard.

촉매 결과Catalyst result

촉매 실험의 결과는 표 1 및 2에 요약되어 있다.The results of the catalyst experiments are summarized in Tables 1 and 2.

Figure pat00030
Figure pat00030

* 본 발명의 화합물 * Compounds of the present invention

올레핀: n-옥텐 (옥세노 게엠베하)Olefin: n-octene (Oxeno GmbH)

용매: 톨루엔Solvent: toluene

리간드/로듐 비율 (L/Rh): 5 : 1The ligand / rhodium ratio (L / Rh): 5: 1

표 1로부터 명백한 바와 같이, 본 발명에 따른 모든 화합물로 매우 우수한 수율이 달성되었다. 또한, 100 ppm에서 60 ppm 및 40 ppm으로의 로듐 농도의 감소는 리간드의 높은 활성에 의해 보상되어, 90% 초과의 수율이 달성되었다.As is evident from Table 1, very good yields were achieved with all the compounds according to the invention. In addition, the reduction of the rhodium concentration from 100 ppm to 60 ppm and 40 ppm was compensated by the high activity of the ligand, yielding a yield of more than 90%.

이는 가능한 한 작은 양의 고가의 로듐 금속을 사용하여 목적 생성물의 여전히 높은 수율을 얻는 것이 바람직하기 때문에 특히 대규모 용도에서 중요한 역할을 한다.This plays an important role, especially in large-scale applications, because it is desirable to obtain a still high yield of the desired product using as little of the expensive rhodium metal as possible.

Figure pat00031
Figure pat00031

* 본 발명의 화합물 * Compounds of the present invention

올레핀: n-옥텐 (옥세노 게엠베하)Olefin: n-octene (Oxeno GmbH)

용매: 톨루엔Solvent: toluene

리간드/로듐 비율 (L/Rh): 5 : 1The ligand / rhodium ratio (L / Rh): 5: 1

표 1에 열거된 네 개의 화합물을 또한 보다 낮은 압력 (20 bar)에서 시험하였다. 이 경우 네 개의 화합물 모두가 또한 매우 우수한 수율을 초래하였다.The four compounds listed in Table 1 were also tested at lower pressures (20 bar). In this case all four compounds also resulted in very good yields.

비교용 화합물 (A) 및 (B)보다 본 발명의 화합물로 상당히 개선된 수율이 달성되었다.Significantly improved yields were achieved with the compounds of the present invention over the comparative compounds (A) and (B).

상기 기재된 실험을 기초로, 진술된 목적이 본 발명에 따른 화합물에 의해 달성됨이 나타날 수 있다.Based on the experiments described above, it can be shown that the stated objectives are achieved by the compounds according to the invention.

Claims (15)

하기 일반 구조 I 또는 II 중 하나를 갖는 화합물.
<화학식 I>
Figure pat00032

<화학식 II>

상기 식에서,
R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -CN, -NH2, -N[(C1-C12)-알킬]2로부터 선택되고;
R9, R10, R11, R12, R13, R14, R15, R16, R17, R18은 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -COO-(C1-C12)-알킬, -CONH-(C1-C12)-알킬, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -COOH, -OH, -SO3H, -NH2, -N[(C1-C12)-알킬]2로부터 선택되고;
언급된 알킬 및 아릴 기는 치환될 수 있다.A compound having one of the following general structures I or II:
(I)
Figure pat00032

&Lt;

In this formula,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -S-alkyl, -S-aryl, halogen, -COO- (C 1 -C 12 ) (C 1 -C 12 ) -alkyl, -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -SO 3 H, -CN, -NH 2, -N [( C 1 -C 12) - alkyl is selected from 2;
R 9, R 10, R 11 , R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl, halogen, -COO- (C 1 - C 12) - alkyl, -CONH- (C 1 -C 12) - alkyl, -CO- (C 1 -C 12) - alkyl, -CO- (C 6 -C 20) - aryl, -COOH, -OH , -SO 3 H, -NH 2, -N [(C 1 -C 12) - alkyl is selected from 2;
The alkyl and aryl groups mentioned may be substituted. 제1항에 있어서, R1, R2, R3, R4, R5, R6, R7, R8이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -N[(C1-C12)-알킬]2로부터 선택된 것인 화합물.The method of claim 1, wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 is -H, - (C 1 -C 12 ) - alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl, halogen, -CO- (C 1 - C 12) - alkyl, -CO- (C 6 -C 20) - aryl, -N [(C 1 -C 12 ) - alkyl; a compound will be selected from the two. 제1항 또는 제2항에 있어서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐, -CO-(C1-C12)-알킬, -CO-(C6-C20)-아릴, -N[(C1-C12)-알킬]2로부터 선택된 것인 화합물.According to claim 1 or 2, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S- aryl , Halogen, -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -N [(C 1 -C 12 ) -alkyl] 2 . 제1항 내지 제3항 중 어느 한 항에 있어서, R1, R2, R3, R4, R5, R6, R7, R8이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐으로부터 선택된 것인 화합물.A compound according to any one of claims 1 to 3, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are -H, - (C 1 -C 12 ) Alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, &Lt; / RTI &gt; 제1항 내지 제4항 중 어느 한 항에 있어서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴, -(C6-C20)-아릴, -S-알킬, -S-아릴, 할로겐으로부터 선택된 것인 화합물. The method according to any one of claims 1 to 4, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12) - alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - aryl, - (C 6 -C 20) - aryl, -S- alkyl, -S-aryl, &lt; / RTI &gt; halogen. 제1항 내지 제5항 중 어느 한 항에 있어서, R1, R2, R3, R4, R5, R6, R7, R8이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴로부터 선택된 것인 화합물.6. Compounds according to any one of claims 1 to 5, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are -H, - (C 1 -C 12 ) alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - a compound selected from one aryl group. 제1항 내지 제6항 중 어느 한 항에 있어서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬, -O-(C6-C20)-아릴로부터 선택된 것인 화합물.The method according to any one of claims 1 to 6, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12) - alkyl, -O- (C 1 -C 12) - alkyl, -O- (C 6 -C 20) - a compound selected from one aryl group. 제1항 내지 제7항 중 어느 한 항에 있어서, R1, R2, R3, R4, R5, R6, R7, R8이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬로부터 선택된 것인 화합물.8. Compounds according to any one of claims 1 to 7, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are -H, - (C 1 -C 12 ) alkyl, -O- (C 1 -C 12) - a compound selected from alkyl to. 제1항 내지 제8항 중 어느 한 항에 있어서, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18이 -H, -(C1-C12)-알킬, -O-(C1-C12)-알킬로부터 선택된 것인 화합물.The method according to any one of claims 1 to 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18 is -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl. 제1항 내지 제9항 중 어느 한 항에 있어서, 하기 일반 구조 1 내지 10 중 하나를 갖는 화합물.
Figure pat00034

Figure pat00035

Figure pat00036
10. A compound according to any one of claims 1 to 9 having one of the following general structures 1 to 10:
Figure pat00034

Figure pat00035

Figure pat00036
 제1항 내지 제10항 중 어느 한 항에 있어서, 일반 구조 I을 갖는 화합물.11. Compounds according to any one of claims 1 to 10, having the general structure I. 제1항 내지 제10항 중 어느 한 항에 있어서, 일반 구조 II를 갖는 화합물.11. Compounds according to any one of claims 1 to 10, having the general structure II. - 제1항 내지 제12항 중 어느 한 항에 따른 화합물, 및
- Rh, Ru, Co, Ir로부터 선택된 금속 원자
를 포함하는 착물.- a compound according to any one of claims 1 to 12, and
- a metal atom selected from Rh, Ru, Co and Ir
&Lt; / RTI &gt; 히드로포르밀화 반응의 촉매작용을 위한, 제1항 내지 제12항 중 어느 한 항에 따른 화합물의 용도.Use of a compound according to any one of claims 1 to 12 for the catalysis of a hydroformylation reaction. 하기 공정 단계:
a) 처음에 올레핀을 충전하는 단계,
b) 제13항에 따른 착물 또는
제1항 내지 제12항 중 어느 한 항에 따른 화합물 및 Rh, Ru, Co, Ir로부터 선택된 금속 원자를 갖는 물질
을 첨가하는 단계,
c) H2 및 CO를 공급하는 단계, 및
d) 반응 혼합물을 가열하여 올레핀을 알데히드로 전환시키는 단계
를 포함하는 방법.The following process steps:
a) initially charging the olefin,
b) a complex according to paragraph 13 or
A compound according to any one of claims 1 to 12 and a compound having a metal atom selected from Rh, Ru, Co, Ir
Lt; / RTI &gt;
c) supplying H 2 and CO, and
d) heating the reaction mixture to convert the olefin to the aldehyde
&Lt; / RTI &gt;
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